Characteristics of pore structure are crucial to oil exploration and development in shale reservoirs, but practical evaluation of shale pore structure remains a longstanding challenge. In this study, based on nuclear magnetic resonance transverse relaxation time (T2) spectra under water-saturated and irreducible conditions, total pore space and moveable fluid space were skillfully determined. Meanwhile, multifractal spectra were used to characterize T2 distributions of total pore space and movable fluid space. The results show characteristic parameters of high probability measure areas of multifractal spectra (multifractal parameters) have strong negative correlations with T2 geometric mean value, and average radii of pore and throat increase with a decrease in the multifractal parameters, indicating the shale reservoirs with low values of the multifractal parameters may have good pore structure. Moreover, clay mineral content has strong positive effects on the multifractal parameters. In contrast, (quartz+feldspar) mineral content negatively influences on the multifractal parameters. Finally, new accurate models for permeability estimation in core scale and well-logging scale of shales are both proposed based on the multifractal parameters, which are also applicable for the other reservoirs. Overall, this study is important and timely for evaluating pore structure and predicting permeability in shale reservoirs.